Patent GB-624364-A (GB)
Title: Improvements in or relating to organo-silicon compounds
IPC: C07F7/08
Filed: 1946-03-08
Abstract: An allyl silicon resin is obtained by hydrolysing an organo-silicon compound of the general formula (H2C=CH-CH2)xRzSiY[4 - (x+z)], wherein x and z are each 1 or 2, the sum of x and z not exceeding 3, R represents a phenyl, alkylphenyl, chlorophenyl or fluorophenyl radical and x represents an ethoxy or chlorine radical, to form the corresponding silicol which is then dehydrated and condensed to form the corresponding silicone. Polymerization through the unsaturated allyl group may also take place.  The dehydration is preferably carried out in the presence of a dehydrating agent, e.g. boric acid esters such as methyl borate, metal halides, the oxides and halides of phosphorus, sulphuric and hydrochloric acids.  The allyl silicones may be added to alkyl and aryl silicones.  Interpolymers may be obtained by carrying the hydrolysis, condensation and dehydration of the above organo-silicon compounds in the presence of one or more organosilicon compounds of the general formula RxSiY(4 - x), wherein R represents a non-polymerizing hydrocarbon group such as an alkyl, phenyl or alkylphenyl group, x has a value 1 to 3 and Y is a halide or an ethoxy group, or by dehydrating and condensing a mixture of the corresponding silicols, or by mixing the corresponding silicones or solutions thereof when they are liquids due to a low degree of polymerization and heating.  The condensation may be carried out to yield a solvent soluble low-viscosity fluid which may be dissolved in a hydrocarbon solvent, e.g. toluene or may be dispersed or emulsified in a volatile liquid carrier such as water with the aid of ammonia, dispersing agents such as sodium alkyl sulphonate ester, or hydrolysed polyvinyl esters and a simple alcohol such as ethyl alcohol.  Finely-divided inorganic materials such as silica flour, bentonite, mica dust, glass powders, calcium fluoride or ceramic powders, graphite, anthracite coal, or coal or petroleum coke may be added to the allyl silicones and the interpolymers thereof.  In examples: dimethyl-silicon diethoxide and allylphenyl silicon diethoxide are treated with concentrated sulphuric acid to yield a low molecular weight interpolymer and may be further polymerized by heat treatment, e.g. in the presence of tertiary butyl perbenzoate, and a mixture of dimethyl-silicon diethoxide, methyl silicon triethoxide and allylphenyl silicon diethoxide in toluene is treated with concentrated sulphuric acid to give a silicone dissolved in toluene.  The Specification mentions that allylphenyl silicon ethoxides may be polymerized through the allyl radical, e.g. by heating in the presence of a catalyst such as benzoyl peroxide, or may be polymerized with other resin-forming substances such as allyl-phthalate.  Specifications 624,361 and 624,363 are referred to.ALSO:Organo-silicon compounds of the general formula <FORM:0624364/IV (b)/1> , wherein x and z are each a number from 1 to 2, the sum of x and z not exceeding 3, R is a phenyl, alkyl-phenyl, chlorophenyl or fluorophenyl radical and Y is chlorine or an ethoxyl radical, are prepared by reacting silicon tetrachloride or ethyl-orthosilicate with an allyl magnesium halide and treating the resulting allyl- or diallyl silicon chloride or silicate with the required aryl magnesium halide.  The organo-silicon compounds may be hydrolysed to form the corresponding silicols which may then be dehydrated and condensed to a silicone.  In examples, allylsilicon ethoxides are prepared and are then separated and allyl silicon triethoxide is reacted with phenyl magnesium bromide to yield allylphenyl-silicon diethoxide.  Similarly the corresponding chlorophenyl-, fluorophenyl- and tolyl-allylsilicon diethoxides may be prepared.  Similarly allyldiphenyl- and diallylphenyl-silicon ethoxides may be prepared.  Silicon tetrachloride may be used as the starting material instead of ethyl orthosilicate.  The organo-silicon compounds may be hydrolysed and condensed in the presence of one or more compounds of the general formula RxSiY(4-n), wherein R represents a non-polymerising hydrocarbon group such as alkyl, phenyl and alkylphenyl radicals, Y is a halide or an ethoxy group and x has a value from 1 to 3.  Specifications 624,361 and 624,363 are referred to.ALSO:Plastic compositions comprise mica flakes or inorganic fibrous materials such as glass or asbestos bound together with a silicone as obtained by hydrolysing and condensing a compound of the general formula (H2=CH-CH2) x(R)zSiY[4-(x+z], wherein x and z are each a number from 1 to 2.  The sum of x and z not exceeding 3, R represents a phenyl, alkylphenyl, chlorophenol or fluorophenyl radicals, and Y represents an ethoxy or chlorine radical, or with a silicone interpolymer as obtained by carrying out the above hydrolysis and condensation in the presence of one or more silicon compounds of the general formula RxSiY(4-x), wherein R represents a non-polymerising hydrocarbon group such as an alkyl, phenyl or alkylphenol group, x has a value from 1 to 3 and Y is a halide or an ethoxy group.  Specifications 624,361 and 624,363 are referred to.